Chemistry - A European Journal,
Год журнала:
2022,
Номер
28(29)
Опубликована: Март 18, 2022
Hydrodefluorination
(HDF)
is
a
very
important
fundamental
transformation
for
conversion
of
the
C-F
bond
into
C-H
in
organic
synthesis.
In
past
decade,
much
progress
has
been
achieved
with
HDF
through
utility
low-valent
metals,
transition-metal
complexes
and
main-group
Lewis
acids.
Recently,
novel
methods
have
introduced
this
purpose
photo-
electrochemical
pathways,
which
are
great
significance,
due
to
their
considerable
environmental
economical
advantages.
This
Review
highlights
fluorinated
compounds
(FOCs)
strategies,
along
mechanistic
insights.
Chemical Society Reviews,
Год журнала:
2023,
Номер
53(1), С. 263 - 316
Опубликована: Дек. 7, 2023
The
employment
of
light
and/or
electricity
-
alternatively
to
conventional
thermal
energy
unlocks
new
reactivity
paradigms
as
tools
for
chemical
substrate
activations.
This
leads
the
development
synthetic
reactions
and
a
vast
expansion
spaces.
review
summarizes
recent
developments
in
photo-
electrochemical
activation
strategies
functionalization
strong
bonds
particularly
carbon-heteroatom
(C-X)
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Дек. 14, 2023
Selective
defluorinative
functionalization
of
trifluoromethyl
group
(-CF3)
is
an
attractive
synthetic
route
to
the
pharmaceutically
privileged
fluorine-containing
moiety.
Herein,
we
report
a
strategy
based
on
photoexcited
copper
catalysis
activate
C-F
bond
di-
or
trifluoromethylated
arenes
for
divergent
radical
C-N
coupling
with
carbazoles
and
aromatic
amines.
The
use
different
ligands
can
tune
reaction
products
diversity.
A
range
substituted,
structurally
diverse
α,α-difluoromethylamines
be
obtained
from
via
carbazoles,
while
interesting
double
ready
difluoromethylated
arenes.
Based
this
success,
carbazole-centered
PNP
ligand
designed
optimal
ligand,
enabling
copper-catalyzed
construction
imidoyl
fluorides
amines
through
functionalization.
Interestingly,
1,2-difluoroalkylamination
styrenes
also
developed,
delivering
γ,γ-difluoroalkylamines,
bioisostere
β-aminoketones,
in
synthetically
useful
yields.
DFT
studies
reveal
inner-sphere
electron
transfer
mechanism
Cu-catalyzed
selective
activation
C(sp3)-F
bonds.
The Chemical Record,
Год журнала:
2024,
Номер
24(3)
Опубликована: Янв. 22, 2024
Abstract
The
increasing
demand
of
organofluorine
compounds
in
medicine,
agriculture,
and
materials
sciences
makes
sophisticated
methods
for
their
synthesis
ever
more
necessary.
Nowadays,
not
only
the
C−F
bond
formation
but
also
selective
cleavage
readily
available
poly‐
or
perfluorine‐containing
have
become
powerful
tools
effective
compounds.
defluorinative
cross‐coupling
trifluoromethyl
alkenes
with
various
nucleophiles
radical
precursors
an
S
N
2’
manner
is
a
convergent
route
to
access
gem
‐difluoroalkenes,
which
turn
react
via
V‐type
reaction.
If
V
reactions
occur
intramolecularly,
dual
allows
facile
assembly
monofluorinated
cyclic
skeletons
structural
complexity
diversity.
In
this
personal
account,
we
summarized
advances
field
on
basis
coupling
cyclization
partners,
including
binucleophiles,
alkynes,
diradical
bearing
nucleophilic
site.
Accordingly,
annulation
can
be
achieved
by
base‐mediated
sequential
2′/S
reactions,
transition
metal
catalyzed
mediated
photoredox
catalysis,
combination
photocatalytic
context
seminal
works
others
field,
concise
summary
contributions
authors
offered.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
61(7)
Опубликована: Дек. 10, 2021
Hydrodefluorination
is
one
of
the
most
promising
chemical
strategies
to
degrade
perfluorochemicals
into
partially
fluorinated
compounds.
However,
controlled
progressive
hydrodefluorination
remains
a
significant
challenge,
owing
decrease
in
strength
C-F
bonds
along
with
defluorination.
Here
we
describe
carbene
strategy
for
sequential
(deutero)hydrodefluorination
perfluoroalkyl
ketones
under
rhodium
catalysis,
allowing
controllable
preparation
difluoroalkyl-
and
monofluoroalkyl
from
aryl-
even
alkyl-substituted
perfluoro-alkyl
high
yield
excellent
functional
group
tolerance.
The
reaction
mechanism
origin
intriguing
chemoselectivity
were
rationalized
by
density
theory
(DFT)
calculations.
Organic & Biomolecular Chemistry,
Год журнала:
2022,
Номер
20(34), С. 6707 - 6720
Опубликована: Янв. 1, 2022
Fluorinated
organic
compounds
are
common
among
pharmaceuticals,
agrochemicals
and
materials.
The
significant
strength
of
the
C-F
bond
results
in
chemical
inertness
that,
depending
on
context,
is
beneficial,
problematic
or
simply
a
formidable
synthetic
challenge.
Electrosynthesis
rapidly
expanding
methodology
that
can
enable
new
reactivity
selectivity
for
cleavage
formation
bonds.
Here,
comprehensive
overview
synthetically
relevant
electrochemically
driven
protocols
activation
functionalization
presented,
including
photoelectrochemical
strategies.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(21)
Опубликована: Март 11, 2022
Carbon-fluorine
bond
activation
of
the
trifluoromethyl
group
represents
an
important
approach
to
fluorine-containing
molecules.
While
selective
defluorinative
functionalization
reactions
CF3
-containing
substrates
have
been
achieved
by
invoking
difluorocarbocation,
difluorocarboradical,
or
difluoroorganometallic
species
as
key
intermediates,
transformations
via
fluorocarbanion
mechanism
only
limited
success.
Furthermore,
enantioselective
transformation
remained
a
formidable
challenge.
Here
we
report
reaction
4-trifluoromethylpyridines
involving
difluoro(pyrid-4-yl)methyl
anion
intermediate,
which
was
developed
based
upon
our
previous
studies
on
N-boryl
pyridyl
chemistry.
In
particular,
asymmetric
defluoroallylation
and
-pyrimidines
could
be
using
Ir-catalysis
forge
difluoroalkyl-substituted
chiral
center.
